77626-29-0Relevant articles and documents
Chemistry of Hydrogen Isocyanide, 9. - Three-Component Cycloadditions with Cyano Complexes
Fehlhammer, Wolf Peter,Rieger, Dirk,Lotz, Sabine,Kernbach, Ulrich,Fuchs, Joachim
, p. 2243 - 2246 (2007/10/02)
A novel and obviously general reaction of the coordinated cyano ligand in - (M = Cr, W) is reported, viz. its high-yield one-step cycloaddition with a great variety of isocyanides and ketones resulting in carbenoid metal complexes of five-membered N,O heterocycles.The structure of the product 1a from -, tert-butyl isocyanide, and diethyl ketone has been elucidated by X-ray diffraction and found to contain a C-bound non-aromatic 4-aminooxazoline with an unprecedented ?-delocalization along the chain which is also evident from severe low-field shifts of the C-2 and C-4 signals in the 13C-NMR spectra.The heterocycles are cleaved off the metal by oxidative decomposition with KMnO4/Fe(NO3)3 to give the corresponding oxazolinones, e.g. 4, with a high potential for biological activity.The general validity of this reactivity pattern for metal cyanides is further demonstrated by the successful incorporation of cyanoiron(II) and -cobalt(III) species in these three-component cycloaddition reactions. - Key Words: Reactions at coordinated cyanide/ Cycloadditions, organometallic/ Carbenoid heterocycles/ Metal-ligand bond cleavage/ Oxazolinone syntheses